Process of dyeing and the products



Patented Mar. 17, 1942 PROCESS OF DYEING AND THE PRODUCTS THUS OBTAINEDJiirgen von Klenck, Frankfort-on-the-Main, Hoclist, and Jose! Niisslein,Frankfort-onthe-Main,

Germany,

assignors to General Aniline & Film Corporation, a corporation ofDelaware No Drawing.

Application July 27, 1939, Serial No. 286,868. In Germany August 3, 1938levelling agents may be added to the dyeing 7 Claims.

The present invention relates to a process of dyeing and to the productsthus obtained.

As is known fibrous material of animal origin may be dyed with aciddyestuffs, for instance, dyestuffs of the anthraquinone,triphenylmethane or azo-series.

This invention is based on the observation that animal fibers and othernitrogenous substances, especially fibrous materials, may be dyed withacid compounds soluble in water, which are obtainable by condensation ofplastic nitrogenous compounds, for instance compounds containingamino-groups, at an elevated temperature and in the presence of anacid-binding agent, with organic compounds containing, besideschromophoric groups, groups which render the products soluble in water,especially acid groups, and groups which can be exchanged, especiallyacid radicals capable of splitting off acid by reaction with thehydrogen atoms of the amino-groups of the plastic material, the lattergroups being eliminated. The dyestufis which may be used in the presentprocess may for instance be made according to the process of applicationSerial No. 212,514, filed June 8, 1938, now Patent No. 2,232,892, in thename of Jiirgen von Klenck for 'Process of dyeing nitrogenous compoundsof high molecular weight and the products thus obtained.

Besides animal fibrous materials such as wool, silk and hair, othernitrogenous compounds, for instance, gelatine, glue, casein, if desiredhardened by means of formaldehyde, may be dyed by this invention; alsoother nitrogenous products of high molecular weight,- for instance,plastic masses, such as condensation products of urea, toluene sulfamideor melamine with formaldehyde, or fibrous materials from such materials,furthermore, animalized cellulose fibers or the like.

The dyestuffs used contain besides acid groups, such as sulfo-groups orcarboxyl groups, and a chromophoric radical, for instance of theanthraquinone, triphenylmethane or azo-series a nitrogenous group ofhigh molecular weight, for instance, the residue of gelatine, casein,wool degradation products or other albuminous substances and nitrogenousplastic masses.

These dyestuffs whose shades depend upon the nature of the condensationcomponents selected are dyed by one or other of the processes usual fordyeing with acid wool dyestuffs, for instance,

in an acid or neutral bath with the aid of sodium sulfate, sodiumbisulfate or ammonium sulfate. The solution obtained by the condensationmay either be used after neutralization directly for dyeing or thedyestufi formed may first be isolated by evaporation or sa lting out andused in a fresh bath for dyeing the material. The usual adjuvants, forinstance, dispersing, wetting and baths.

The dyeings thus produced are distinguished by a good evenness. Theirproperties of fastness depend in high degree upon the nature of thecomponents that are condensed to form the dyestufi. The fastness of thedyeings especially the fastness to wet processing may be enhanced by anafter-treatment with agents which effect a polymerization, agglomerationor hardening of the nitrogenous bodies of high molecular weight whichhave been used in making the dyestuff, for instance, gelatine.

Suitable agents for the after-treatment are those of tanning action,such as chromium salts and formaldehyde. The after-treatment may beapplied at ordinary or raised temperature on wet or dry dyeings with orwithout addition of a catalyst. If plastic masses capable of beinghardened are used in the manufacture of the dyestuffs, the dyeing needonly be heated in order to harden it and thus to improve the fastness.

The following examples serve to illustrate the invention, but they arenot intended to limit it thereto:

1. 1 gram of 1-bromo-2-anthraquinonesulfonic acid is treated with thesame quantity of gelatine, 2 grams of 'sodium bicarbonate, 1 gram ofcalcined sodium carbonate and 0.1 gram of crystallized'copper sulfate incc. of water at boiling temperature until the brown solution", which wasat first colorless, no longer, changes its color; this happens afterabout 3-4 hours. The solution thus obtained is neutralized.

calculated on the weight of the goods, and 10 cc. of the neutralizeddyestufl solution. 10 grams of wool are dyed in the usual manner in thisbath for 1 hour at the boil. An even dyeing of the full brown isobtained. The fastness to wetprocessing may be improved byafter-treating the goods with an acid solution, at raised temperature,containing 2 per cent. of formaldehyde or 1 per cent. of potassiumbichromate, calculated on the weight .of the goods.

Instead of the condensation product from bromanthraquinonesulfonic acidand gelatine there may be used the condensation product from gelatineand l-amino-4-iodanthraquinone- 2.6-disulfonicacid (violet dyeing) ,orl-chloro- 4-nitro-8-anthraquinonesulfonic acid (blue dyeing) or theazo-compound from ortho-chloraniline and 1-hydroxy-4-naphthalenesulfonicacid (red dyeing).

fonic acid is treated for 4 hours at boiling temperature with the samequantity of gelatine and 2 grams of sodium bicarbonate, 1 gram ofcalcined sodium carbonate and 0.1 gram of copper bromide in 100 cc. ofwater. The dark brown solution obtained is neutralized by means of anacid and the condensation product formed is precipitated by addingsaturated sodium chloride solution. After filtering and drying about 1.7grams of dyestutf are obtained.

A dyebath is prepared by means of a Per cent Formic acid Sodium sulfatecrystals... Dyestuff l7 Oxethylation product from oleylalcohol and vmols of ethylene oxide 1 10 grams of wool are dyed in this boiling bathfor 1 hour. The wool is dyed a clear deep brown shade.

3. 1 gram of 1-amino-4-bromo-2-anthraqui none-carboxylic acid is treatedwith the same quantity of gelatine and 2 grams of sodium bicarbonate, 1gram of crystallized sodium car-. bonate, 0.2 gram of crystallizedcopper sulfate and 3 cc. of pyridine in 100 cc. of hot water. The deepviolet solution obtained is neutralized by means of an acid and /10 ofthe solution is used for preparing a dyebath containing Per centSulfuric acid 4 Sodium sulfate crystals 10 10 grams of wool are dyed adeep violet shade after 1 hours boiling in this bath.

4. 1 gram of 1-ani1ido-4-iodo-2-anthraquinone-sulfonic acid is treatedfor 2 hours with the same quantity of gelatine, 2 grams of sodiumbicarbonate, 1 gram of crystallized sodium carbonate, 0.2 gram ofcrystallized copper sulfate, 3 cc. of pyridine and 0.1 gram of copperbromide in 100 cc. of water at boiling temperature. The deep bluesolution obtained is neutralized and /10 of the solution is added to adyebath prepared with 5 per cent. of acetic acid and 10 per cent. ofcrystallized sodium sulfate. 10 grams of wool are dyed in this bath aclear deep blue shade. The fastness of this very even dyeing may beimproved by after-treatment with potassium bichromate and acetic acid,the shade assuming a somewhat greener coloration.

5. 1 gram of 1-anilido-4-iodo-2-anthraquinone-sulfonic acid is treatedfor 5 hours at boiling temperature with 2 grams of a water-solubleproduct, obtainable by condensation of urea with formaldehyde, in anaqueous solution containing Grams Sodium bicarbonate 2 Calcined sodiumcarbonate 1 Crystallized copper sulfate 0. 1

The deep-blue solution is treated with saturated sodium chloridesolution whereupon the condensation product, a blue dyestufi, isprecipitated.

A dyebath is prepared with 7 Per cent Sulfuric acid 4 Crystallizedsodium sulfate 10 Oleic acid methyl tauride 0.5

/10 of the blue dyestufi obtained is added. 10 grams of wool are dyed aclear vivid blue by boiling it in this bath for 1 hour. The dyeing istreated for 10 minutes at 130 C. in a drying oven whereupon its fastnessto wet-processing is improved.

Per cent Ammonium sulfate 5 Crystallized sodium sulfate -10 Afterboiling for one hour 10 grams of wool are dyed a vivid brown.

7. 1 gram of 1-bromo-2-anthraquinonesulfonic acid is treated accordingto Example 1 at boiling temperature with the same quantity of gelatine,

2 grams of sodium bicarbonate, 1 gram of calcined sodium carbonate and0.1 gram of crystallized copper sulfate in cc. of water, until the brownsolution which was at first colorless, no longer changes its color: thishappens after about 3-4 hours. The solution thus obtained isneutralized.

A dyebath is prepared which contains Water cc 200 Sulfuric acid --percent 4 Sodium sulfate crystals do 10 calculated on the weight of thegoodsand /10 of the neutralized dyestufi solution obtained as describedabove. 10 grams of fibers produced on the basis of casein are dyed inthe usual manner in this bath for 1 hour at the boil. An even dyeing ofa full brown is obtained. The fastness to wet-processing may be improvedessentially by after-treating the goods, at raised temperature, with anacid solution containing 2 percent. of formaldehyde or 11 2 per cent. ofpotassium bichromate, calculated on the weight of the goods.

A similar dyeing is obtained. when cuprammonium silk is dyed in thedyebath described, which has been animalized by incorporating acondensation product from chlorine-hard paraffin and ethylenediamine(of. British Patent No. 440,647). Also this dyeing which isdistinguished by a good evenness, may be improved in its fastness towet-processing by the indicated aftertreatment.

8.1 gram of 1.4-dichloro-B-anthraquinonesulfonic acid is treatedaccording to Example 2 for 4 hours at boiling temperature with the samequantity of gelatine and 2 grams of sodium bicarbonate, 1 gram ofcalcined sodium carbonate and 0.1 gram of copper bromide in 100 cc. ofwater. The dark brown solution obtained is neutralized by means of anacid and the dyestufi formed is precipitated by adding saturated sodiumchloride solution. After filtering and drying about 1.7 grams ofdyestuif are obtained.

A dyebath is prepared by means of this bath for 1 hour at boilingtemperature, which has been animalized by incorporating a condensationproduct from a bromide of a mixture of alcohols of high molecular weightwith polymeric ethyleneimine (cf. French Patent No.

10 grams of viscose artificial silk are dyed in 810,395). The fiber isdyed a clear deep brown shade.

9. 1 gram of 1-anilido-4-iodo-2-anthraquiof crystallized sodiumcarbonate, 0.2 gram of crystallized copper sulfate, 3 cc. of pyridineand 0.1 gram of copper bromide in 100 cc. of water at boilingtemperature. The deep blue solution obtained is neutralized and {e orthe solution is added to a dyebath prepared with 5 per cent. of aceticacid and '10 per cent. of crystallized sodium sulfate. Viscoseartificial silk, which was animalized by incorporating casein, is dyedin this bath clear blue shades. The iastness of this very even dyeingmay be improved essentially by after-treatment with potassium bichromateand acetic acid, the shade assuming a somewhat greener coloration.

We claim: g

1. The process which comprises dyeing fibrous materials containing aminogroups with acid dyestuffs obtained by reacting plasticmaterialscontaining amino groups, at an elevated temperature and in the presenceof an acid-binding agent, with organic compounds containing chromophoricgroups, water-solubilizing acid groups and acid radicals the acidradicals being capable of splitting oif acid by reaction with thehydrogen atoms of the amino groups of the plastic material andsplittingoff only said acid radicals by vated temperature and in the presence 0!an acidbinding agent, with a-halogen-anthraquinonesulfonic acids.

4. The process which comprises dyeing wool with acid dyestufis obtainedby reacting plastic materials containing amino groups, at an elevatedtemperature and in the' presence of an acidbinding agent, withd-halogen-anthraquinonesulionic acids.

5. The process which comprises dyeing wool with acid 'dyestufls obtainedby reacting gelatine and in the presence at an elevated temperat ofanacid-binding agent, with u-halogenanthraatoms of the amino groups of theplastic material and splitting 01! only said acid radicals by the stufisobtained by reacting plastic materials conltaming amino groups, at anelevated temperature and in the presence of an acid-binding agent, withd-halogen-anthraquinonesultonic acids.

3. The process which comprises dyeing fibrous materials containing aminogroups with acid dyestufis obtained by reacting gelatine, at anelequinonesulfonic acids.

6. The process which comprises dyeing fibrous materials containing aminogroups with acid dyestufls obtained by reacting plastic materialscontaining amino groups at an elevated temperature and in the presenceof an acid-binding agent, with organic compounds containing chromophoricgroups, wateii-solubilizing acid groups and acid radicals the acidradicals being capable of splitting 0!! acid by reaction with'thehydrogen reaction and after-treating the dyeings in order to enhancetheir fastness with agents which effect a polymerization of the plasticmaterials.

7. Fibrous materials containing amino groups dyed with acid dyestuffsobtained by reacting plastic materials containing amino groups at anelevated temperature and inthe presence of an acid-binding agent, withorganic compounds containing chromophoric groups, water-solubilizingacid groups and acid radicals theacid radicals being. capable ofsplitting ofl acid by reaction with the hydrogen atoms of the aminogroups of the plastic material and splitting of! only said

